Metaphosphates as dough improvers

ABSTRACT

1. A BREAD DOUGH COMPOSITION CONTAINING FROM 2-50 PARTS PER MILLION BASED ON THE WEIGHT OF FLOUR PRESENT IN SAID DOUGH OF A METAPHOSPHATE WHEREIN SAID COMPOSITION CONTAINS AN AMOUNT OF A CONVENTIONAL OXIDIZING AGENT SELECTED FROM THE GROUP CONSISTING OF ACETONE PEROXIDE, AZODICARBONAMIDE, CHLORINE DIOXIDE, POTASSIUM BROMATE AND POTASSIUM IODATE EFFECTIVE TO AGE SAID FLOUR.

United 'States Patent Office Patented Oct. 8, 1974 3,840,668 METAPHOSPHATES AS DOUGH IMPROVERS Robert R. Joiner, Belleville, and Frederick D. Vidal,

Englewood Cliffs, NJ., assignors to Pennwalt Corporation, Philadelphia, Pa. No Drawing. Filed Sept. 13, 1971, Ser. No. 180,157 Int. Cl. A21d 2/02, 2/04, 2/24 US. Cl. 426-22 5 Claims ABSTRACT OF THE DISCLOSURE STATEMENT OF THE INVENTION This invention relates to a composition useful for making bread. The invention more specifically relates to bread, and a dough composition for making bread containing a uniquely low but effective quantity of a metaphosphate (e.g. 2-50, preferably 5-10, parts per million parts of flour).

The baked bread formed from the dough composition of the present invention is characterized by generally increased bread volume, an improved volume to weight ratio, and especially, improved (i.e. a fine and uniform) grain and texture compared with a loaf from a comparative formula containing no metaphosphate; the baked loaf has improved crumb color, and better overall bread appearance. The improved results are achieved in all bread-making processes including the conventional (straight or sponge) or continuous process. Additionally it is found that the improvement is enhanced when the metaphosphate is used in known systems of bread baking in combination with a conventional amount of an oxidizing agent, such as azodicarbonamide and bromate. Improvement is noted not only in the final product when using the dough of the present invention but it has been observed that the metaphosphate dough handles better during bread making processes, i.e. it is easier to mold and is stronger as evidenced by fewer collapses compared to dough in which no such additive is present.

PRIOR ART In the prior art, it is known to use metaphosphates, orthophosphates and pyrophosphates as additives to edible materials. For a number of specific purposes, it is recognized that metaphosphates are preferred over the orthophosphates or pyrophosphates. It is also known to add metaphosphates to flours such as wheat flour (see US. 2,365,438) and to add metaphosphates as a part of a leavening agent for cake and biscuit doughs (see US. 2,366,857), in order to improve properties. The use of the metaphosphates has also been extensively discussed as a whipping agent in instant cake mixes and as an antioxidant for a wide variety of food products. In all of the prior art compositions substantially large quantities of metaphosphates are required. It is also known to add metaphosphates to dough for bread baking (see French Patent 726,324) at relatively large proportions (e.g. 100-500 p.p.m.) well beyond the recommended limit for the composition of the present invention.

Metaphosphates Examples of metaphosphates suitable for use in the present invention include sodium hexametaphosphate, sodium trimetaphosphate, sodium tripolyphosphate (all available from a number of chemical manufacturers), Calgon SQ phosphate (available from Calgon Company) which represent linear, polylinear and polycyclic metaphosphate compositions having a wide range of molecular weights which generally are described as powdered or amorphous, glassy materials. Thus the term metaphosphate, as used herein includes the polyphosphate produced by heating simple metaphosphate to eliminate H O, as is well-known in the art, and the glassy phosphate produced by fusion and rapid cooling of the metaphosphate.

Oxidizing Agent Particularly enhanced results are obtained upon baking a bread dough containing 2-50 parts per million metaphosphate and also a conventional amount of an oxidizing (i.e. maturing) agent such as an azodicarbonamide containing composition of which Maturox (a commercially available composition) is an example, potassium bromate, potassium iodate, chlorine dioxide and acetone peroxide formulations. These agents are added in conventional quantities varying from about 5-125 p.p.m., based on flour present, depending on the baking procedure used and the particular oxidizing agent used.

THE EXAMPLES-IESTS AND RATINGS USED The invention will be better understood by reference to the Examples which are cited to illustrate the invention and not to limit it in any manner. The loaves produced are rated on the basis of the volume of the loaves (which varies with the particular type of processing) and inside loaf characteristics such as grain and texture which are scored comparatively with a perfect score being based on 100. In the tested systems a typical volume for a g. loaf in the straight dough system and using untreated flour is about 600 ml.; in the sponge and continuous mix systems for a 450 gm. loaf, the typical is about 2750 ml. In interpreting the results reported in the Examples one must realize that truly comparative baking results are possible only among each days runs with the same flour since if one attempts to run identical bakes on successive days using identical materials, there will always be some variation from bake to bake due to variations in temperature of the room or the temperature of the water, or to small variations in proof box or oven temperatures or to slight variations in manual or mechanical handling and the like. Similarly the degree of response varies widely with the particular flour used in a test bake. Since in the various series of bakes reported herein in different runs a number of different flour samples are used, varying degrees of response occur; thus only results of the same run within each Table are comparable.

In the Examples the processes employed (known as straight, sponge, and continuous mix systems and variations thereof) are not critical to the success of the invention and any system of baking can be used. The details of these commercial systems are well known in the art. All parts per million (p.p.m.) reported are based on the weight of the flour used. The ratio reported in the Tables is obtained by dividing the volume of the loaf in milliliters by the weight of the loaf in grams. Loaf volumes are reported in milliliters.

EXAMPLE 1 In a straight dough system 100 g. pup loaves are formed and baked using a formula which omits the use of oxidizing agents. The straight system uses a typical formulation:

100 g. Flour g. Sugar 3 g. Yeast 0.25 g. Yeast Food 2 g. Salt VariableWater 5 and the method generally involves a single step process in which all the ingredients are mixed together in a single batch before fermenting, molding, and proofing. The phosphate additive, when used, is added at the dough-up stage. The various phosphates and the parts per million employed (in parenthesis) is indicated in Table I, along with the observed results for four independent baking series (i.e. A, B, C and D). Control samples (which contain no added phosphate) are included in each series for comparative purposes.

TABLE I Bunloaf Additive Volume Ratio Score A-1 None (control) 750 5.20 93.0 .A-2 -.do 730 5.28 93.0 A4)--. Sodium tripolyphosphate (10).- 780 5. 45 93. 5 A-4 o 760 5. 35 93.5 A-5.-. Sodium hexametaphosphate (10). 760 5.85 94. 0 A-6 -do 745 5. 93. 5 11-7... Sodium hexametaphosphate (5) 760 5.58 94.0 25 .A-8--. SQ, phosphate (10) 745 5. 17 94.0 A-9.-. Insoluble sodium metaphosphate (10) 780 5. 40 94.0 A-10 Insoluble sodium metaphosphate (5).- 750 5. 50 94. 0 14-11.. Sodium trlmetaphosphate (5) 750 5. 42 94.0 .A12.- Sodium phosphate, tribasie (5) 740 5. 44 93. 0 3-1... None (control) 820 5.80 94.0 B-2.-. Sodium trimetaphosphate (50) 845 5. 95 94. 5 13-3-" Insoluble sodium metaphosphate 50)- 865 6.15 95. 5 13-4..- Sodium hexametaphosphate (50) 880 5. 91 95. 0 B5 Sodium trimetaphosphate (25) 810 5. 78 95.0 B-6-.. Insoluble sodium metaphosphate (25). 860 6. 10 95.5 B-7-.- Sodium hexametaphosphate (25) 855 6. 10 95.5 13-8... Insoluble sodium metaphosphate (5)-. 815 5. 81 94.0 3-9... Sodium hexametaphosphate (5) 810 5.70 94. 5 0-1... None (control) 740 5.27 93.0 0-2-.- Insoluble sodium metaphosphate 735 5. 15 93.0 O3 Insoluble sodium metaphosphate (30)- 745 5. 21 93. 5 0-4... Insoluble sodium metaphosphate (20). 750 5. 32 93.0 C-5 Insoluble sodium metaphosphate (10)- 765 5. 42 93.0 C6 Insoluble sodium metaphosphate (5).. 750 5. 25 93. 0 D-l. None (control) 760 5. 51 93. 0 D2 Sodium hexametaphosphate (4) 790 5. 71 98. 5 4o D3 Sodium hexametaphosphate (2) 770 5. 42 93. 5

1 An orthophosphate.

The effectiveness of the metaphosphate additives even at the extremely low concentrations at which they are used and in the difiiculty controllable art of bread making can be seen from the data of Table I. Run A illustrates the effectiveness of various additives within the preferred concentration range; of the nine loaves to which metaphosphate was added, seven are equal or superior to each control sample in all three measured variables while in the remaining two loaves (Nos. 6 and 8) superiority in at least two parameters is present compared to the average value of the controls.

Sample A-12 (wherein the additive is an orthophosphate) compared with A-7, A-lO and A-ll (containing metaphosphate at the same 5 p.p.m. level) illustrates the unexpected superiority of the metaphosphates to the orthophosphates.

Runs B and C demonstrate eifectiveness of higher concentrations of metaphosphate Within the scope of the invention while Run D illustrates effective use of concentrations of metaphosphate below the preferred limit.

EXAMPLE 2 In this example, the composition and technique of Example l is repeated, however, either azodicarbonamide (ADA) potassium bromate, or both (WaTox) and metaphosphate (as additive) are mixed into the flour prior to dough-up. The additive, when used, with parts per million indicated in parenthesis, is reported in Table II along with observed results for two runs, E and F.

Comparison of loaves in run E containing the same quantity of oxidizer (e.g. 17-21, 11, 8 and 6) illustrates the enhancing effect of the metaphosphate particularly within the preferred range of metaphosphate concentration. The same effect is apparent when one compares the results of the metaphosphate-containing loaves (3-5 and 7-10) of run F with the control loaves containing only oxidizer (2 and 6) and the control containing no additive (1).

TAB LE II Run-loaf Additive Volume Ratio Score E-l None (Control. 760 5. 51 93. 0 15-2.. 740 5. 28 93. 0 13-3.. 885 6. 22 96. 0 15-4.. 845 6. 05 95. 5 13-5.. 830 5. 91 95. 0 13-6.. 850 5. 85 96. 0 E- 875 6. 24 96. 5 E8 915 6. 38 97. 0 13-9.. 900 6. 33 97. 0 E-lO- 880 6. 29 96. 5 E-11 905 6. 41 97. 0 13-12. 830 5. 88 95. 5 E-l3. 850 6. O0 95. 5 E-14- 865 6.06 95. 0 El5 870 6. 12 96. 0 E46- 850 6. 00 96. 5 E47. 880 6. 12 96. 0 16-18. 850 5. 93 95. 0 E19 870 6. 08 95. 5 E20 875 6. 11 96. 0 E=2l 885 6. 22 96. 5 E22-. 860 6. 09 96. 5 E23 845 6. 02 96.0 E-24- 840 6. 03 95. 5 E-25- 855 6. 05 96. 0 F1 720 5. 02 93. 0 F2 830 5. 79 96.0 F-3 840 5. 88 96. 5 F4 840 5. 86 96. 0 F5 810 5. 70 96. 5 F-6 Potass um bromate (10) 795 5. 95.0 F7 Potass um bromate (10) plus sodium hexametaphosphate (5) 880 5. 75 96. 5 F-8. Potassium bromate (10) plus sodium hexametaphosphate (10)--." 820 5. 77 95. O F9. Potass um bromate (10) plus sodium hexametaphosphate (30)- 20 5. 95. 0 F-lO Potassium bromate (10) plus sodium hexametaphosphate (40) 830 5. 83 95. 5

l The first number withi t e p e t esis i dicates ro ate a d the ec nd, D a i p-P- EXAMPLE 3 of 5 p.p.m., except loaf 6 which contains 10 p.p.m.) in

This Example illustrates the addition of other phosg g q System i phates to flour in the sponge system of baking, using the Serva Ions are repor e m a e pound loaf method. The results are shown in Table III.

The sponge method uses a typical formulation: 5

TABLE IV Run-loaf Additive Volume Ratio Score H-l None (control) 2, 640 5.73 93.5 H-2 ADA 2, 755 5.98 94. H-3 ADA 2,760 6. 05 95.5 11-4- ADA plus insoluble metaphosphate 2, 850 6. 13 96. 0 11-5. ADA plus insoluble sodium metaphosphate- 2, 720 5. 90 96. 0 H-6 ADA plus sodium trimetaphosphate 2, 750 5. 99 96. 0 H-7 .do 2, 770 6. 00 96. 0 131-8 ADA plus sodium hexametaphosphate 2, 750 6. 00 96. 5 H9 -do 2, 800 6. 09 96. 5

EXAMPLE 5 Sponge Dough 15 420 280 This Example illustrate the effect of potassium bro- 252 variable mate (at a level of 10 p.p.m.) and iodate (at a level of i 2 5 p.p.m.) as oxidizing agents in combination with metaphosphates (at a level of 5 p.p.m.) in the sponge system of Example 3 except that the additive, when present Milk powder, g Q: 21 is added 60% by weight to the sponge and by weight to the dough-up, observations being reported in Table V.

TABLE V Run-loaf Additive Volume Ratio Score None (control). 2,680 5.90 94.0 Potassium bromate 2, 820 6. 25 95. 0 Potassium inflate 2, 910 6. 43 95. 5 Potassium bromate plus insoluble soium metaphosphate 2, 860 6. 31 95. 0 Potassium bromate plus sodium hexametaphosphate g, (23% --d i Potas sium iodate plus insoluble sodium metaphosphate- 2, 940 6. 96. 0 1-8 Potassium iodate plus sodium hexametaphosphate 2,880 0.14 96. 5

and the method generally involves the mixing of of EXAMPLE 6 the flour with Water Yeast and Yeast food followed by a This Example shows the results of a combination of fermentation p ri d f hours this case 41/2 hours) phosphates (at a 5 p.p.m. level) and chlorine dioxide (at to form a fermented dough or sponge. At the second or 35 a 10 level) as oxidizing agent in the dough-11p Stage, t e 1 9 is combined Wlfll unfefmfinted system of Example 3 except that all additive is added to dough formed from the remaining flour and other ingredth sponge dough. The results are shown in Table VI.

TABLE VI Run-loaf Additive Volume Ratio Score 1-1 None (control) 2,725 5.97 93.5 .T2.. Chlorine dioxide 2,820 6.23 96.0 1%.. Calcium phosphate tribasic 2,730 5.97 94.0 J-4 Chlprin?1 itiioxide plus insoluble sodium meta- 2,880 6.36 95.5

I) 081) 8 e. 1-5 Chlprine dioxide plus sodium hexametaphos- 2,780 6.05 95.5

D 3. e. J-fi Chlorine dioxide plus sodium trlmetaphosphate- 2,810 6.16 97. 0

NoTE.-* orthophosphate.

ients, mixed and followed with an additional short EXAMPLE 7 fermentation period. The final dough mixture is then This Example shows the results of the addition of phosmolded, shaped, proofed and baked. 50 phates (at a 5 p.p.m. level) and acetone peroxide (at a In making the loaves of this example, the additive 125 p.p.m. level) as oxidizing agent in the sponge syswhen present, is added to the flour; each additive is present tern of Example 3 where the additive is added to the at a level of 5 parts per million parts of the flour used. sponge dough. The results are reported in Table VII.

TABLE VII Run-loaf Additive Volume Ratio Score None (control)... 2,650 5.70 93.0 Acetone peroxide 2,660 5.75 93.5 Acetone peroxide plus 2, 780 5.95 96.0

phosphate. K-i Aeeltone peroxide plus sodium hexametaphos- 2,850 6.12 96.5

ate. do 2,905 6.25 95.5 Acetone peroxide plus sodium trimetaphosphate. 2,795 6. 05 96.5 K-7 Aegetone peroxide plus calcium phosphate tri- 2,790 6. 05 94.0

N OTE.* =orthophosphate. TABLE III EXAMPLE 8 Run-1081 Additive Volume Ratio Score This Example gives the efiect of addition of different G4 Nonmontmn 2715 M5 9% metaphosphates a level o 5 p-pnawa x (3-2 Insoluble sodium metaphosphate- 2,780 6.03 94.0 (trade name for a commercial product containm-g both 21 gig azodicarbonamide and potassium bromate) as the oxidiz- 6.22 94.0 ing agent in a continuous mix process. The results are reported in Table VHI. WaTox is added at a dosage level EXAMPLE 4 to contribute 30 parts per million potassium bromate This example illustrates mixtures of azodicarbonamide and 15 parts per million azodicarbonamide. Each additive (at a level of 10 p.p.m.) and metaphosphate (at a level is added to the dough.

A typical baking formulation is used in this continuous mix system as shown below:

and the method generally involves the fermentation of a broth for 2 /2 hours, after which the broth is combined with the flour and shortening in a premixer after which it passes into a continuous dough mixer which brings it to the proper degree of development. The dough is divided, panned, proofed and then baked.

TABLE XI Runloaf Additive Volume Ratio Score -1".-. None (control) 820 5. 80 94. 0 O2. Sodium hexamctaphosphate (25).". 855 6.10 95. 5 O3.. Sodium hexametaphosphate (50).". 830 5. 91 95.0 0-4... Sodium hexametaphosphate (100) 830 5. 85 94. 0 P-l. None (control) 775 5. 45 93.0 P-2. ADA (20) 885 6.22 96.0 P-3. ADA (20) plus sodium hcxameta- 900 6.33 97.0

phosphate (2). P4.. ADA (20) plus sodium hexametw 895 6.30 97. 0

phosphate (250). Q1. None (control).. 770 5.37 93.0 Q-2. ADA 850 6. 01 95.5 Q,3 ADA (15) plus sodium hexameta- 880 6.12 96.0

phosphate 10). Q-4 ADA (15) plus sodium hexameta- 885 6.22 96.5

phosphate (50). 15 R1 None (control) 730 5.05 93.5 R-2. Potassium bromate (10) 795 5.00 95.0 R-S. Potassium bromate 10) plus sodium 830 5. 75 96.0

hexametaphosphate (5).

11-4. Potassium bromate (10) plus sodium 810 5. 70 96.0

hexametaphosphate (100).

R-5, Potassium bromate (10) plus sodium 825 5. 72 95. 5

hexametaphosphate (500).

TABLE VIII Runloaf Additive Volume Ratio Score L-1 Walox 2, 760 6.12 98.0

L2 WaTox plus sodium tn'metaphos- 2,660 5.97 99.0

p e e.

L3. walllor plus sodium hexametaphos- 2,620 5.85 99.5

p a e.

L4 WaTox plus insoluble sodium meta- 2,610 5.83 100.0

phosphate.

L-5 Waklloxminussodium hexametaphos- 2,670 5.91 99.5

p ate.

EXAMPLE 9 This Example shows the efiects of the azodicarbonamide (at a 30 p.p.m. level) and metaphosphate (at a 5 p.p.m. level) in the continuous mix system of Example 8. The results are shown in Table IX.

This Example shows the activity of chlorine dioxide, i.e. Dyox (at a level of 10 p.p.m.) treated flour, in combination with metaphosphates (at a level of 5 p.p.m.) using the continuous mix systems of Example 8 wherein potassium bromate, i.e. Br (at a level of 20 p.p.m.) and potassium iodate, i.e. I (at a level of 5 p.p.m.) are used as supplemental oxidizing agents.

TABLE X Runloaf Additive Volume Ratio Score N1 Dyox plus Br-I 2, 660 5. 91 99. 0 N2 Dyox plus Br-I plus sodiumtrimet- 2, 670 6.00 99. 5

aphosphate. N-3 Dyox plus Brl'. plus sodium hexa- 2, 640 5.88 100.0

metaphosphate. N-4 do 2, 650 5. 95 90. 5

EXAMPLE 1 1 This Example compares results achieved at high and low concentrations of metaphosphate oxidizer combinations. The system corresponds to the straight dough system of Example 1 wherein 100 gram pup loaves are baked. The numbers in parenthesis after each additive, where present, indicates the concentration of that component in parts per million based on the weight of flour used to make the loaf. The observations for four runs are reported in Table XL The results reported in Table XI indicate that when higher than 50 p.p.m. concentration of metaphosphate is used, the improvement tends to be lost or to plateau in some instances.

EXAMPLE 12 The procedure of Example 11 is followed in a customerservice laboratory (where particular eifort is made to duplicate commercial operations) for five runs in which azodicarbonamide, i.e. ADA (at a level of 18 p.p.m., except in run U where a level of 31 p.p.m. is used) alone and in combination with various concentrations (indicated by the numeral in parenthesis and representing p.p.m.) of sodium hexametaphosphate. The observations are reported in Table XII and the best loaf or loaves in each run selected by the observer is indicated by the asterisk.

4 TABLE XII Runat Additive Volume Score S1- ADA 2, 550 86 S2* ADA plus sodium hexamctaphosphate (10). 2, 700 88 8-3..... ADA plus sodium hexametaphosphate (20). 2, 550 87 5 T1- ADA ,875 86.0 T-2* ADA plus sodium hexametaphosphate (10) 2, 800 87. 0 T3* ADA plus sodium hexametaphosphate (20) 2, 900 86. 5 T- i- ADA plus sodium hexametaphosphate 2, 850 86. 5 T-5. ADA plus sodium hexametaphosphate (100) 2 850 86. 0 U1 ADA 2, 575 83.0 U-2 ADA plus sodium hexametaphosphate (10) 2, 550 84. 0 U-3 ADA plus sodium hexametaphosphate (20) 2, 625 83.0 ADA plus sodium hexametaphosphate (40) 2, 700 85.0 ADA plus sodium hexametaphosphate (50)- 2, 450 84. 0 DA 2, 650 86. 0 ADA plus sodium hexametaphosphate (100) 2, 600 85. 0 ADA plus sodium hexametaphosphate (250) 2, 625 84. 0 ADA 2, 750 86. 0 ADA plus sodium hexametaphosphate (1 ,800 88. 0 ADA plus sodium hexametaphosphate (20)- 2, 750 87.0 ADA plus sodium hexametaphosphate r30) 2, 725 86. 5

Many equivalent modifications of the invention described herein will be apparent to those skilled in the art from a reading of the above without a departure from the inventive concept.

What is claimed is:

1. A bread dough composition containing from 2-50 parts per million based on the weight of flour present in said dough of a metaphosphate wherein said composition contains an amount of a conventional oxidizing agent selected from the group consisting of acetone peroxide, azodicarbonamide, chlorine dioxide, potassium bromate and potassium iodate effective to age said flour.

2. The composition of claim 1 wherein the metaphosphate is a linear, polylinear, or polycyclic phosphate.

3. The composition of Claim 2 wherein the metaphosphate is sodium hexametaphosphate.

4. In the method of making bread products by a process which comprises combining dough forming ingredients References Cited FOREIGN PATENTS 5/1932 'France 99-91 11/1968 Great Britain 426-62 JAMES R. HOFFMAN, Primary Examiner US. Cl. X.R. 

1. A BREAD DOUGH COMPOSITION CONTAINING FROM 2-50 PARTS PER MILLION BASED ON THE WEIGHT OF FLOUR PRESENT IN SAID DOUGH OF A METAPHOSPHATE WHEREIN SAID COMPOSITION CONTAINS AN AMOUNT OF A CONVENTIONAL OXIDIZING AGENT SELECTED FROM THE GROUP CONSISTING OF ACETONE PEROXIDE, AZODICARBONAMIDE, CHLORINE DIOXIDE, POTASSIUM BROMATE AND POTASSIUM IODATE EFFECTIVE TO AGE SAID FLOUR. 